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    Bhushan 1995

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    REVIEW ARTICLE Nanotribology: friction, wear and lubrication at the atomic scale Bharat Bhushan, Jacob N. Israelachvili & Uzi Landman Friction, wear and lubrication between materials in contact are of fundamental importance in many pure and applied sciences. Owing to the development of experimental and computer- simulation techniques for studying these phenomena at the atomic scale, an understanding is beginning to emerge of the molecular mechanisms of tribology in thin films and at surfaces. UnpeRstaNpine the atomic processes occurring at the inter- face of two materials when they are brought together separated or moved with respect to one another is central to many techno- logical problems, including adhesion, contact formation, fric- tion, wear, lubrication, nanoindentation, fracture and machining’ +, At most interfaces of technological relevance, con tact occurs ai numerous asperities'. Consequently, the import- ance of investigating single asperity contacts in studies of the fundamental micromechanical and tribotogical properties of sur faces and interfaces has been long recognized”. The recent emergence and proliferation of proximal probes, in particular tip-based microscopes (the scanning tunnelling microscope and the atomic-force microscope) and the surface-force apparatus, and of computational techniques for simulating. tip-surface interactions and interfacial properties, has allowed systematic investigations of interfacial problems with high resolution as well as ways and means for modifying and manipulating nanoscale structures. These advances provide the impetus for research aimed at developing a fundamental understanding of the nature land consequences of the interactions between materials on the atomic scale, and they guide the rational design of materials for technological applications. In short, they have led to the appearance of the new field of nanotribology’®", which pertains to experimental and theoretical investigations of interfacial pro- cesses on scales ranging from the atomic and molecular to the ‘microscale. ‘The surface-force apparatus (SFA)'™™, the scanning tunnel- ling microscope (STM)", the atomic-force and friction-foree microscopes (AFM and FFM)", as well as the quartz micro- balance technique”, are widely used in nanotribological studies. The SFA was developed in the late 1960s and is commonly employed to study both static and dynamic properties of molecu- larly thin films sandwiched between two molecularly smooth surfaces. The STM, developed in 1981, allows imaging of electr- cally conducting surfaces with atomic resolution, and has been used for imaging of clean surfaces as well a of lubricant ‘molecules. The introduction of the atomic-force microscope in 1985 provided @ method for measuring ultra-small forces between a probe tip and an electrically conducting or insulating surface, and has been used for topographical measurements of surfaces on the nanoscale, as well as for adhesion and electro- static fore measurements. Subsequent modifications of the AFM led to the development of the friction-force microscope (FFM). designed for atomic-scale and microscale studies of friction. This instrument measures forces transverse to the surface. The AFM is also being used for investigations of wear, indentation, detcc- tion of transfer of material, boundary lubrication, and nanofab- rication and machining, Meanwhile, significant progress in understanding the fundamental nature of bonding and inter- actions in materials, combined with advances in computer-based ‘modelling and simulation methods, have allowed theoretical studies of complex interfacial phenomena with high resolution in space and time'*"®, Such simulations provide insights into atomic-scale energetics, structure, dynamics, thermodynamics, transport and theological aspects of tribological processes. NATURE - VOL 374 - 13 APRIL 1995 Furthermore, these theoretical approaches guide the interpreta- tion of experimental data and the design of new experiments, provide a framework for analysis and development of unifying concepts, and enable the prediction of new phenomena based ‘on atomistic principles. Here we review several of the principal theoretical and experi- ‘mental aspects of research in nanotribology. The nature of inter~ actions between (wo surfaces brought close together, and those between two surfaces in contact as they are separated, have been studied experimentally with the surface-force apparatus. This hhas led to a basic understanding of the normal forces between surfaces, and of the dramatic way in which these are modified by the presence of an intervening medium such as a liquid or a polymer ‘brush’ adsorbed or chemically grafted to the surfaces The frictional properties of such systems have been studied by ‘moving the surfaces laterally, and such experiments have pro- vided insights into the molecular-scale operation of lubricants such 5 thin liquid or polymer films. Often, these lubricants ‘behave in ways that would not be predicted on the basis of their bulk-scale behaviour alone. Complementary to these studies are those in which the AFM and FFM are used as a ‘model asperity’ in contact with a solid surface. These experiments have demonstrated that the relationship between friction and surface topography is not always simple or obvious. AFM studies have also revealed much about the nanoscale nature of intimate con- tact—of indentation and wear. Computer simulations of tip surface interactions at the atomic scale have shown the surface need not behave as an elastic medium but can deform plast- ically, for example leading to ‘necking’ between surface layers and the probe tip. Surface-force studies of thin films ‘The surface-force apparatus has long been used to measure both static'™”” and dynamic!™**"* forces between smooth, macro- scopic surfaces, As with AFMs and most other force-measuring devices, forces are determined from the defection of a spring, and displacements are measured using some optical, electrical, capacitive or strain-gauge technique. The prineiple of operation of SFAs (Fig. 1) is thus fairly simple; the challenge comes in ‘measuring very weak forces, sub-microscopie surface geometries and surface separations at the dngstrém level. Static (equilibrium) properties of thin liquid films. The inter- molecular interaction potential or force function between (wo surfaces interacting in or across a liquid medium ean be attrac- tive, repulsive, ‘oscillatory’ or a more complex function of separ- ation. Recent experiments and theoretical studies (mainly computer simulations) have shown that the structure of the liquid molecules and of the confining surfaces are very important in determining what the force function will be® **. Furthermore, two crystalline surfaces may induce a liquid to solidify (freeze) when the gap thickness is close toa small multiple of the molecu- lar diameter (Fig. 1, bottom left)” *°"*". The oscillatory force- function resulting from such an interaction is illustrated in Fig. 1 (top left)". 607 REVIEW ARTICLE FIG. 1 Mustration of the principle of the surtaceforce ‘apparatus (SFA) for measuring the normal forces, F, and {ncuon or shear forces, f, between two smooth surfaces ‘of area A separated by a thin liquid fm of thickness O (els 18-24), An optical interference technique allows the Shapes of the surfaces and their separation, D, to Be accurately monitored during foree and friction measure ‘ments. Typical contact area Ais 100 um”, and gap thick esses can range from one molecular layer (D= a= 4 A, where ois the molecular dismeter) to thousands of ngstrdms. An oscillatory force function, FO}, ‘ypicaly measured across simple liquids is shown at top lek, ane The structure adopted by molecules in ultra-thin films is wer erally very different from their bulk structure; other thin-film properties may also be very different. The freezing point may be higher or lower, depending on whether the ‘epitaxial interaction of the confined molecules with the two surfaces is cooperative or disruptive” ““* and molecular relaxation times can be many orders of magnitude longer than in the bulk"? Tes also interesting to note that even though one surface can have an effect on the structure of the liquid molecules adjacent to it", the effect of two confining surfaces is generally much more dramatic, and can produce a greater variety of interfacial (non-bulkclike) structures—amorphous, solid or liquid-crystal line-—each of which gives rise (oa different type of force function 4s well as to different dynamic properties, as described below. Dynamic and shear properties of thin films. The force between two surfaces across a liquid or lubricant fluid tells us whether two surfaces, when pressed together, will come into adhesive contact or remain separated by-a thin, liqud-like layer" This is crucially important for understanding the behaviour that results when one of the surfaces is made to move laterally or to shear past the other, as occurs during frictional and lubricated sliding. For example, if the two surfaces are in true molecular contact when sliding begins, their friction will be high and their adhesion may be strong enough to tear them apart. If, however, the surfaces are separated by one or more molecular layers of the fluid, and if this cushioning film remains in the liguid-Hke state during sliding, this may ensure that the friction force f will ‘be low and that sliding will proceed smoothly (Fig. 1, bottom right). Experiments have shown that even one layer of water molecules, approximately 0.25 nm thick, between two hydro- philic surfaces can be sufficient to reduce the interfacial friction force to a very low value” On the other hand, ifthe surface-Auid interactions induce the liquid molecules to solidify. the molecular configuration during sliding will be much more complicated. In such cases the film alternately melts and freezes during the motion’” “67 ®, as shown schematically in the lower part of Fig. 1; the resulting two common 'ypes of Trcton traces (ction force versus time: f(2) are shown in the oscilloscopes at the bottom fof the figure. During siaing, two smooth surfaces usualy emain in one of the adhesive minima of the force func tion, although the kinetic film thickness D, is usually slighty diferent from the equilorium or state thickness, >. friction is of the ‘stick-slip’ type. Sticking occurs in the frozen state, giving rise to the static friction force, f,. and slipping ‘curs in the shear-induced molten state giving rise tothe kinetic friction force, f,. The real situation, even for the simplest sur- faces and liquids, is actually much more complicated than shown in Fig. 1: the direction of sliding is generally at some angle to the surface lattices, the two surface lattices are not generally in registry, the surface and liquid molecules have different diam- eters, and they are generally not even spherical. This complexity leads to complex force functions and friction-time relationships. Even for quite complex force functions, however, recent experic ments have shown that the forces of friction and adhesion are closely related” Shear-induced ordering transitions, Recent experiments and computer simulations have shown that different types of ordered structures may occur during frictional sliding’™*". The idea of a ‘structure’ being induced by motion is an unfamiliar concept, but ‘shear-induced ordering’ is at the heart of what goes on in such thin films. Different types of ordered states can appear depending on the temperature, load and sliding velocity, and dynamic phase transitions between these states can also occur during sliding, each giving rise to a complex stick-slip friction pattern, Such effects are now believed to underlie many other apparently unrelated dynamic processes involving. stick-slip motion, such as earthquakes, the sound of a violin (and other instruments), the squeaking of doors, and sensory perception (of touch and even taste)" Figure 2 shows some of the dynamic film structures that can arise during the sliding of two surfaces that contain boundary layers of surfactant molecules. In general, solid-ike films exhibit stick-slip motion, amorphous-like films exhibit high friction due {o the molecular interdigitations and entanglements occurring between the two surfices, and liquid-tike films exhibit low, vis- couslike friction with smooth sliding. These dynamic states are not intrinsic properties of w shearing film (in the way that they are for bulk condensed phases at any given temperature and pressure): they depend not only on the temperature and pressure NATURE » VOL 374 - 13 APRIL 1995 REVIEW ARTICLE ‘Amorphous regime Fiction force ee Solidike regime Liquide regime == Siding velocity, » Temperature > % u % Salid “Amorphous Liquid $ ve Ss Sue | Supariinetic siding] i FIG. 2 Schematic ustrations of aiferent types of dynamic thin-lm structures that can arise during lubricated sliding. Top, dynamic phase diagram representation of friction force (or rate of energy dissigation) 28 a function of temperature or siding velocty (adapted from refs 61 ‘and 62). Under certain favourable coneitions involving surface grates Chain molecules”, the entangled molecules at the interface may undergo ‘shearinduced ordering. when they disentangle and become ‘aligned; at the same time the friction force drops signiianty (super. kinetic friction), ‘of applied load, but also on the relative sliding velocity of the two shearing surfaces (which is not necessarily the same at the velocity of the drive: see Fig. 1). Higher sliding speeds make the film more solid-ike, whereas slower speeds make it behave more like a liquid. This principle, known as time-temperature super- position, has recently been found to be very useful in understand> ing the effects of time, temperature, load and other variables on the complex molecular processes occurring at a shearing inter- Face and the resulting friction forces" Attaining desirable friction properties. The attainment of low adhesion, low friction and low wear (surface damage) is usually ‘a desirable practical goal. But there are cases where the aim may be to attain a constant friction force (with load or speed) oF even a high friction, as occurs in the case of clutch fluids. By judiciously choosing the right lubricant fluid and, in some cases, by chemically grafting chain-like molecules such as surfactants” co polymers" to surfaces (these are known as boundary lub- ricants), itis becoming possible to control the frictional proper: ties of moving components in machines and other devices. For NATURE » VOL 374 » 13 APRIL 1995 ‘example, the grafting of certain surfactant molecules at a certain coverage to surfaces has been found” to produce films that can undergo a dynamic first-order transition from a high friction state to a low friction state (Fig. 2). The advantage of such 2 lubricant system is that no lubricant fluid is actually ever applied ‘or needed—the surfaces are self-lubricating in the sense that they are processed right from the start to carry their own lubricant layer with them; also, very small quantities of material are needed so that material costs should not be prohibitive even for fairly expensive lubricants. This is a good example of how recent research in the field of molecular tribology is opening up pos- sibilities for creating new types of lubricant systems. AFM/FFM studies of tribological processes Adhesion“ *, friction”, wear"! °°" and tubrica- tion®®” * at ‘the interface between two solids with and with- out liquid films have been studied using the AFM and FFM. Surface roughness is routinely measured using the AFM™ *, and both instruments have been used for measuring. clastic plastic mechanical properties””""7*7""" *, At most solid-solid interfaces of technological relevance, contact occurs at numerous asperities' “'*""; a sharp AFM/FFM tip sliding on a surface simulates just one such contact'*"*. For measurements of surface roughness friction forces and nanoscale scratching and wear, a microfabricated square-pyramidal SisN, oF silicon tip with a tip radius ranging from 10 to SOnm is generally used"® at loads ranging from 10 to 150nN, For measurements of microscale scratching and wear, and for nanoindentation hardness measure- ments and nanofabrication, a three-sided pyramidal single- crystal naturai-diamond tip with a tip radius of about 100:nm is generally used! at relatively high loads, ranging from 10 to 150 wN. Surface roughness, adhesion and friction. Solid surfaces, ire spective of their method of formation, generally contain surface irregularities. When two nominally flat surfaces are placed in contact, surface roughness causes contact to occur at discrete contact points. Deformation occurs at these points, and may be either elastic or plastic, depending on the nominal siress, surface roughness and material properties. The sum of the areas of all the contact points constitutes the real area of contact, and for ‘most materials at normal loads, this will be only a small fraction of the area that would be in contact ifthe surfaces were perfectly smooth, In general, this real area of contact must be minimized to minimize adhesion, frietion and wear" Characterizing surface roughness is therefore important for predicting and understanding the tribological properties of solids in contact. The AFM has been used to measure surface rough ress on length scales from nanometres to mierometres"™* ", Sur- face roughness most commonly refers to the variations in the height of the surface relative to a reference plane”. Commonly measured roughness parameters. such as rm.s. surface height and peak-to-valley distance, are found to be scale-dependent for any given surface. The topography of most engineering surfaces is fractal, possessing a self-similar structure over a range of scales, BY using fractal analysis one can characterize the rough ness of such surfaces with two seale-independent fractal param eters D and C. which provide information about roughness at all length scales". ‘These wo parameters are instrument- independent and are unique for each surface. D (generally rang- ing from 1 (o 2) primarily relates to distribution of different frequencies in the surface profile, and C to the amplitude of the surface height variations at all frequencies. A fractal model of elastic-plastic contacts" has been used to predict whether con- tacts experience elastic or plastic deformation, and to predict the statistical distribution of contact points To study friction mechanisms on an atomic scale, a well char- acterized, freshly cleaved surface of highly oriented pyrolytic graphite (HOPG) has been studied by Mate e” al.” and Ruan and Bhushan" ‘The atomic-scale friction force of HOPG exhibited the same periodicity as the corresponding topography 609 REVIEW ARTICLE (Fig. 3a), but the peaks in friction and those in topography were displaced relative to each other" (Fig. 3h). A Fourier expansion of the interatomic potential was used to calculate the conserv- ative interatomic forces between atoms ofthe FFM tip and thos fof the graphite surface. Maxima in the interatomic forces in the normal and lateral directions do not occur at the same location, which explains the observed shift between the peaks in the lateral force and those in the corresponding topography. Furthermore the observed local variations in friction force can be explained by variation in the intrinsic lateral force between the sample and the FFM tip", and these variations may not necessarily occur as a result of atomic-scale stck-slip processes!" Frictional forces of HOPG have also been studied on micro: metre scales", Local variations in the microscale friction of cleaved graphite are observed, which arise from structural changes that occur during the cleaving process". The cleaved HOPG surface is largcly atomically smooth but exhibits line- shaped regions in which the coefficient of friction is more than order of magnitude larger. Transmission electron microscopy indicates that the line-shaped regions consist of graphite planes of different orientation, as well as of amorphous carbon. Differ- ences in friction can also be seen for organic mono- and mult- layer films”, which again seem to be the result of structural variations in the films. These measurements suggest that the FFM can be used for structural mapping of the surfaces. FFM measurements can be used to map chemical variations as indica~ ted by the use of the FFM with a modified probe tip to map the spatial arrangement of chemical functional groups in mixed organic monolayer films”. Here, sample regions that had stronger interactions with the functionalized probe tip exhibited larger friction Local variations in the microscale friction of scratched LX tovearay 0) Fon 610 ificant, and seen to depend on the local surface slope rather than the surface height distribution ®”" Directionality in friction is sometimes observed on the macro: scale; on the microscale this is the norm'®**”"-" This is because ‘most ‘engineering’ surfaces have asymmetric surface asperities, so that the interaction of the FFM tip with the surface is depen? dent on the direction of the tip motion, Moreover, during surface finishing processes material can be transferred. preferentially onto one side of the asperities, which also causes asymmetry and directional dependence. Reduction in local variations and in directionality of frictional properties therefore requires careful ‘optimization of surface roughness distributions and of surface- finishing processes. Table I shows the coefficients of friction measured for two surfaces on micro- and macroscales. The coefficient of friction FIG. 3 a, Grey-scale plots of surface topography tle) {and friction profiles (right) of a1

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